Classifications

• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
  • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
  • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
  • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
  • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
  • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/133302—Rigid substrates, e.g. inorganic substrates
• • G—PHYSICS
  • G11—INFORMATION STORAGE
  • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
  • G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
  • G11B5/62—Record carriers characterised by the selection of the material
  • G11B5/73—Base layers, i.e. all non-magnetic layers lying under a lowermost magnetic recording layer, e.g. including any non-magnetic layer in between a first magnetic recording layer and either an underlying substrate or a soft magnetic underlayer
• • G—PHYSICS
  • G11—INFORMATION STORAGE
  • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
  • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
  • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
  • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
  • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
  • G11B7/253—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates
  • G11B7/2531—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates comprising glass
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2201/00—Glass compositions
  • C03C2201/06—Doped silica-based glasses
  • C03C2201/08—Doped silica-based glasses containing boron or halide
  • C03C2201/10—Doped silica-based glasses containing boron or halide containing boron
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2203/00—Production processes
  • C03C2203/10—Melting processes

Definitions

• the present invention relates to an alkali-free glass suitable as a glass substrate for various displays, for photomasks, for supporting electronic devices, for information recording media, for flat antennas, and the like.
• glass used for various displays, photomasks, electronic device supports, information recording media, flat antenna glass plates (glass substrates), especially glass plates with thin films of metals or oxides formed on their surfaces The following characteristics (1) to (4) are required.
• the glass contains an alkali metal oxide, the alkali metal ions diffuse into the thin film and deteriorate the film properties of the thin film, so that the glass does not substantially contain alkali metal ions.
• the strain point is high so that the deformation (thermal shrinkage) accompanying the deformation of the glass plate and the stabilization of the glass structure can be minimized.
• buffered hydrofluoric acid used for etching SiO x and SiN x
• chemical liquid containing hydrochloric acid used for etching ITO and various acids (nitric acid used for etching metal electrodes) , Sulfuric acid, etc.) and resist stripping solution alkali and the like.
• BHF buffered hydrofluoric acid
• ITO chemical liquid containing hydrochloric acid used for etching ITO
• various acids nitric acid used for etching metal electrodes
• Sulfuric acid etc.
• resist stripping solution alkali and the like.
• a glass having a small average thermal expansion coefficient is required for the purpose of increasing the temperature raising / lowering rate of the heat treatment during the production of the liquid crystal display to increase the productivity or the thermal shock resistance.
• the average thermal expansion coefficient of glass is too small, the number of film formation processes such as a gate metal film and a gate insulating film during the production of a liquid crystal display increases, and the warpage of the glass increases. There are problems such as occasional problems such as cracks and scratches, and a large shift in the exposure pattern.
• a glass having a high specific modulus Youngng's modulus / density
• An object of the present invention is to provide a glass that can suppress deformation such as warping of a glass substrate, is excellent in moldability, and has a low burden on manufacturing equipment.
• the alkali-free glass of the present invention that achieves the above object has an average thermal expansion coefficient of 30 ⁇ 10 ⁇ 7 to 43 ⁇ 10 ⁇ 7 / ° C. at 50 to 350 ° C., a Young's modulus of 88 GPa or more, and a strain point of 650 to 725 ° C., temperature T 4 at which viscosity is 10 4 dPa ⁇ s is 1290 ° C. or lower, glass surface devitrification temperature (T c ) is T 4 + 20 ° C.
• T 2 at which viscosity is 10 2 dPa ⁇ s is 1680 °C or less, 62 to 67% of SiO 2 in terms of mol% based on oxide, Al 2 O 3 of 12.5 to 16.5%, 0 to 3% of B 2 O 3 8-13% MgO 6-12% CaO, 0.5-4% SrO, Containing 0 to 0.5% of BaO, MgO + CaO + SrO + BaO is 18 to 22%, and MgO / CaO is 0.8 to 1.33.
• the specific elastic modulus may be 34 MN ⁇ m / kg or more.
• the density may be 2.60 g / cm 3 or less.
• the glass surface devitrification viscosity ( ⁇ c ) may be 10 3.8 dPa ⁇ s or more.
• the glass transition point may be 730 to 790 ° C.
• the value represented by the following formula (I) may be 4.10 or more. (7.87 [Al 2 O 3 ] -8.5 [B 2 O 3 ] + 11.35 [MgO] + 7.09 [CaO] + 5.52 [SrO]-1.45 [BaO]) / [SiO 2 ]
• the value represented by the following formula (II) may be 0.95 or more. ( ⁇ 1.02 [Al 2 O 3 ] +10.79 [B 2 O 3 ] +2.84 [MgO] +4.12 [CaO] +5.19 [SrO] +3.16 [BaO]) / [SiO 2 ] ... Formula (II)
• the value represented by the following formula (III) may be 5.5 or less. (8.9 [Al 2 O 3 ] +4.26 [B 2 O 3 ] +11.3 [MgO] +4.54 [CaO] +0.1 [SrO] ⁇ 9.98 [BaO]) ⁇ ⁇ 1 + ([ MgO] / [CaO] -1) 2 ⁇ / [SiO 2 ]
• SnO 2 may be contained in an amount of 0.5% or less in terms of mol% based on the oxide.
• the ⁇ -OH value may be 0.05 to 0.5 mm ⁇ 1 .
• the compaction may be 100 ppm or less.
• the equivalent cooling rate may be 5 to 500 ° C./min.
• One embodiment of the alkali-free glass of the present invention may be a glass plate having at least one side of 1800 mm or more and a thickness of 0.7 mm or less.
• One embodiment of the alkali-free glass of the present invention may be manufactured by a float process or a fusion process.
• the display panel of the present invention has the alkali-free glass of the present invention.
• the semiconductor device of the present invention has the alkali-free glass of the present invention.
• the information recording medium of the present invention has the alkali-free glass of the present invention.
• the planar antenna of the present invention has the alkali-free glass of the present invention.
• the present invention it is possible to provide a glass that can suppress deformation such as warping of a glass substrate, is excellent in moldability, and has a low burden on manufacturing equipment.
• composition range of each component of the glass is expressed in mol% based on the oxide.
• a numerical range indicated by “Numerical value A to Numerical value B” indicates a range including the numerical value A and the numerical value B as the minimum value and the maximum value, respectively, and means a numerical value A or more and a numerical value B or less.
• the content of SiO 2 is 62% or more, preferably 62.5% or more, more preferably 63% or more, particularly preferably 63.5% or more, and most preferably 64% or more.
• the content of SiO 2 exceeds 67%, the solubility of the glass tends to decrease, the Young's modulus decreases, and the devitrification temperature tends to increase. Therefore, the content of SiO 2 is 67% or less, preferably 66.5% or less, more preferably 66% or less, and particularly preferably 65.7% or less.
• Al 2 O 3 increases the Young's modulus to suppress deflection, suppress the phase separation of the glass, improve the fracture toughness value, and increase the glass strength.
• the content of Al 2 O 3 is 12.5% or more, preferably 12.8% or more, more preferably 13% or more. If the content of Al 2 O 3 exceeds 16.5%, the solubility of the glass becomes poor, the strain point increases, and the devitrification temperature may increase. Therefore, the content of Al 2 O 3 is 16.5% or less, preferably 16% or less, more preferably 15.7% or less, still more preferably 15% or less, and particularly preferably 14.5% or less. Preferably it is 14% or less.
• B 2 O 3 is not an essential component, it may be contained in an amount of 3% or less because it improves BHF resistance, improves the melting reactivity of the glass, and lowers the devitrification temperature.
• the content of B 2 O 3 is 3% or less, preferably 2.5% or less, more preferably 2.2% or less, still more preferably 2% or less, particularly preferably 1.7% or less, most preferably 1.5% or less.
• MgO increases the Young's modulus without increasing the specific gravity, it can suppress the deflection by increasing the specific elastic modulus, and also increases the fracture toughness value and increases the glass strength. MgO also improves solubility. If the content of MgO is less than 8%, these effects are hardly exhibited, and the thermal expansion coefficient may be too low. Therefore, the content of MgO is 8% or more, preferably 8.2% or more, and more preferably 8.5% or more. However, when there is too much MgO content, devitrification temperature will rise easily. Therefore, the content of MgO is 13% or less, preferably 12% or less, more preferably 11% or less, further preferably 10.5% or less, particularly preferably 10% or less, and most preferably 9.7% or less. It is.
• CaO is characterized in that it has a specific modulus higher than that of MgO in alkaline earth metals and does not excessively lower the strain point, and also improves the solubility in the same manner as MgO. Further, CaO has a feature that it is difficult to increase the devitrification temperature compared to MgO. If the content of CaO is less than 6%, these effects are difficult to appear. Therefore, the CaO content is 6% or more, preferably 7% or more, more preferably 8% or more, and further preferably 9% or more. If the content of CaO exceeds 12%, the average thermal expansion coefficient becomes too high, and the devitrification temperature becomes high, which tends to cause devitrification during the production of glass. Therefore, the content of CaO is 12% or less, preferably 11% or less, more preferably 10% or less.
• the SrO content improves the solubility without increasing the devitrification temperature of the glass, but if the SrO content is less than 0.5%, this effect is less likely to appear. Therefore, the SrO content is 0.5% or more, preferably 1% or more, more preferably 1.2% or more, and further preferably 1.5% or more. SrO has the above effect lower than BaO, and if the content of SrO is excessively increased, the effect of increasing the specific gravity is rather superior, and the average thermal expansion coefficient may be too high. Therefore, the SrO content is 4% or less, preferably 3% or less, more preferably 2.5% or less, and still more preferably 2% or less.
• BaO is not an essential component, but may improve the solubility without increasing the devitrification temperature of the glass. Therefore, it may be contained in the alkali-free glass of this embodiment. However, when the content of BaO is excessive, the specific gravity increases, the Young's modulus decreases, and the average thermal expansion coefficient tends to be too large. Therefore, the content of BaO is 0.5% or less. It is preferable that the alkali-free glass of this embodiment contains substantially no BaO. In the present specification, “substantially does not contain” means that it is not contained other than inevitable impurities mixed from raw materials or the like, that is, it is not intentionally contained.
• the content of BaO in the case of substantially not containing BaO is, for example, 0.3% or less, preferably 0.2% or less, more preferably 0.1% or less, and further preferably Is 0.05% or less, particularly preferably 0.01% or less.
• RO MgO + CaO + SrO + BaO
• MgO / CaO is 0.8 or more, preferably 0.85 or more, more preferably 0.9 or more, and further preferably 0.92 or more.
• MgO / CaO is 1.33 or less, preferably 1.3 or less, more preferably 1.25 or less, further preferably 1.2% or less, particularly preferably 1.1% or less, and most preferably 1 .05% or less.
• the alkali-free glass of the present embodiment does not substantially contain alkali metal oxides such as Li 2 O, Na 2 O, and K 2 O.
• the total content of alkali metal oxides when substantially not containing alkali metal oxides is, for example, 0.5% or less, preferably 0.2% or less, more preferably 0. 0.1% or less, more preferably 0.08% or less, still more preferably 0.05% or less, and most preferably 0.03% or less.
• the alkali-free glass of the present embodiment substantially contains P 2 O 5 so as not to cause deterioration of properties of a thin film such as a metal or an oxide provided on the glass plate surface. It is preferable not to contain.
• the content of P 2 O 5 in the case of not containing the P 2 O 5 substantially is, for example, 0.1% or less.
• the alkali-free glass of the present embodiment does not substantially contain PbO, As 2 O 3 , or Sb 2 O 3 .
• the content of PbO, As 2 O 3 , and Sb 2 O 3 when substantially not containing PbO, As 2 O 3 , or Sb 2 O 3 is, for example, 0.01% or less, Preferably it is 0.005% or less.
• the alkali-free glass of this embodiment is one of ZrO 2 , ZnO, Fe 2 O 3 , SO 3 , F, Cl, and SnO 2.
• the total amount of seeds or more may be 2% or less, preferably 1% or less, more preferably 0.5% or less.
• F is a component that improves the solubility and clarity of glass.
• the content of F is preferably 1.5% or less (0.43% by mass or less).
• SnO 2 is also a component that improves the solubility and clarity of glass. If the inclusion of SnO 2 in the alkali-free glass of the present embodiment, the content of SnO 2 is less than 0.5% (1.1 mass%) is preferred.
• the ⁇ -OH value of the alkali-free glass of the present invention is preferably 0.05 to 0.5 mm ⁇ 1 .
• the ⁇ -OH value is an index of the water content in the glass.
• the absorbance of the glass sample with respect to light having a wavelength of 2.75 to 2.95 ⁇ m is measured, and the maximum value ⁇ max of the absorbance is determined as the thickness (mm ) Divided by When the ⁇ -OH value is 0.5 mm ⁇ 1 or less, compaction described later is easily achieved.
• the ⁇ -OH value is more preferably 0.45 mm ⁇ 1 or less, more preferably 0.4 mm ⁇ 1 or less, more preferably 0.35 mm ⁇ 1 or less, even more preferably 0.3 mm ⁇ 1 or less, particularly preferably 0.28 mm -1 or less, and most preferably 0.25 mm -1 or less.
• the ⁇ -OH value is 0.05 mm ⁇ 1 or more, the glass strain point described later can be easily achieved.
• the ⁇ -OH value is more preferably 0.08 mm ⁇ 1 or more, more preferably 0.1 mm ⁇ 1 or more, further preferably 0.13 mm ⁇ 1 or more, particularly preferably 0.15 mm ⁇ 1 or more, and most preferably 0.18 mm ⁇ 1 or more.
• the alkali-free glass of this embodiment preferably has a value represented by the following formula (I) of 4.10 or more. (7.87 [Al 2 O 3 ] -8.5 [B 2 O 3 ] + 11.35 [MgO] + 7.09 [CaO] + 5.52 [SrO]-1.45 [BaO]) / [SiO 2 ]
• the value represented by the formula (I) is an index of Young's modulus. If this value is less than 4.10, the Young's modulus becomes low.
• the value represented by the formula (I) is more preferably 4.15 or more, further preferably 4.2 or more, particularly preferably 4.25 or more, and most preferably 4.3 or more. .
• [Al 2 O 3 ], [B 2 O 3 ], [MgO], [CaO], [SrO], [BaO], and [SiO 2 ] are each mol% based on the oxide. It means the content of Al 2 O 3 , B 2 O 3 , MgO, CaO, SrO, BaO, SiO 2 in the display. The same applies to the following formulas (II) and (III).
• the alkali-free glass of this embodiment preferably has a value represented by the following formula (II) of 0.95 or more. ( ⁇ 1.02 [Al 2 O 3 ] +10.79 [B 2 O 3 ] +2.84 [MgO] +4.12 [CaO] +5.19 [SrO] +3.16 [BaO]) / [SiO 2 ] ...
• the value represented by the formula (II) is an index of the strain point. If this value is less than 0.95, the strain point becomes high.
• the value represented by the formula (II) is more preferably 1.0 or more, further preferably 1.05 or more, and particularly preferably 1.1 or more.
• the alkali-free glass of this embodiment preferably has a value represented by the following formula (III) of 5.5 or less. (8.9 [Al 2 O 3 ] +4.26 [B 2 O 3 ] +11.3 [MgO] +4.54 [CaO] +0.1 [SrO] ⁇ 9.98 [BaO]) ⁇ ⁇ 1 + ([ MgO] / [CaO] -1) 2 ⁇ / [SiO 2 ]
• the value represented by the formula (III) is an index of the glass surface devitrification viscosity ( ⁇ c ), and when this value exceeds 5.5, the glass surface devitrification viscosity ( ⁇ c ) becomes low.
• the value represented by the formula (III) is more preferably 5.1 or less, further preferably 4.8 or less, particularly preferably 4.5 or less, and most preferably 4.3 or less. .
• the alkali-free glass of this embodiment has an average coefficient of thermal expansion at 50 to 350 ° C. of 30 ⁇ 10 ⁇ 7 / ° C. or higher.
• a gate metal film such as copper and a gate insulating film such as silicon nitride may be sequentially stacked on an alkali-free glass substrate.
• the average coefficient of thermal expansion at 50 to 350 ° C. is less than 30 ⁇ 10 ⁇ 7 / ° C., the difference in thermal expansion from the gate metal film such as copper formed on the substrate surface becomes large, and the substrate becomes inactive. There is a risk of problems such as film peeling.
• the average thermal expansion coefficient at 50 to 350 ° C. is 43 ⁇ 10 ⁇ 7 / ° C. or less.
• the average coefficient of thermal expansion at 50 to 350 ° C. is preferably 42 ⁇ 10 ⁇ 7 / ° C. or less, more preferably 41.5 ⁇ 10 ⁇ 7 / ° C. or less, still more preferably 41 ⁇ 10 ⁇ 7 / ° C. or less. 5 ⁇ 10 ⁇ 7 / ° C. or less is particularly preferable, and 40.3 ⁇ 10 ⁇ 7 / ° C. or less is most preferable.
• the Young's modulus of the alkali-free glass of this embodiment is 88 GPa or more.
• substrate by an external stress is suppressed.
• the substrate can be prevented from warping when it is formed on the surface of the glass substrate.
• warpage of the substrate when a gate metal film such as copper or a gate insulating film such as silicon nitride is formed on the surface of the substrate is suppressed. Further, for example, deflection when the size of the substrate is increased is also suppressed.
• the Young's modulus is preferably 88.5 GPa or more, more preferably 89 GPa or more, further preferably 89.5 GPa or more, particularly preferably 90 GPa or more, and most preferably 90.5 GPa or more. Young's modulus can be measured by an ultrasonic method.
• the alkali-free glass of this embodiment has a strain point of 650 to 725 ° C.
• the strain point is preferably 685 ° C. or higher, more preferably 690 ° C. or higher, further preferably 693 ° C. or higher, particularly preferably 695 ° C. or higher, and most preferably 698 ° C. or higher.
• the strain point is too high, it is necessary to increase the temperature of the slow cooling device accordingly, and the life of the slow cooling device tends to decrease.
• the strain point is preferably 723 ° C. or less, more preferably 720 ° C. or less, further preferably 718 ° C. or less, particularly preferably 716 ° C. or less, and most preferably 714 ° C. or less.
• the temperature T 4 at which the viscosity becomes 10 4 dPa ⁇ s is 1290 ° C. or less.
• the alkali free glass of this embodiment is excellent in a moldability.
• the temperature at the time of molding the glass of the present embodiment can be lowered to reduce volatilized substances in the atmosphere around the glass, thereby reducing defects.
• glass can be shape
• T 4 is preferably 1287 ° C. or less, more preferably 1285 ° C.
• T 4 can be determined as the temperature at which the viscosity is 10 4 d ⁇ Pa ⁇ s by measuring the viscosity using a rotational viscometer in accordance with the method prescribed in ASTM C 965-96. In the examples described later, NBS710 and NIST717a were used as reference samples for apparatus calibration.
• the alkali-free glass of the present embodiment has a glass surface devitrification temperature (T c ) of T 4 + 20 ° C. or lower.
• T c glass surface devitrification temperature
• the alkali free glass of this embodiment is excellent in a moldability. Moreover, it can suppress that the crystal
• Glass surface devitrification temperature (T c) is preferably T 4 + 10 ° C. or less, more preferably T 4 + 5 ° C. or less, T 4 ° C. more preferably less, T 4 -1 ° C.
• the glass surface devitrification temperature (T c ) and the glass internal devitrification temperature (T d ) can be determined as follows. That is, put crushed glass particles in a platinum dish, heat-treat for 17 hours in an electric furnace controlled at a constant temperature, and using an optical microscope after the heat treatment, the maximum temperature at which crystals are deposited on the glass surface The lowest temperature at which crystals do not precipitate is measured, and the average value is defined as the glass surface devitrification temperature (T c ).
• the maximum temperature at which crystals precipitate inside the glass and the minimum temperature at which crystals do not precipitate are measured, and the average value is defined as the glass internal devitrification temperature (T d ).
• the viscosity at the glass surface devitrification temperature (T c ) and the glass internal devitrification temperature (T d ) can be obtained by measuring the viscosity of the glass at each devitrification temperature.
• the specific elastic modulus (Young's modulus (GPa) / density (g / cm 3 )) of the alkali-free glass of this embodiment is preferably 34 MN ⁇ m / kg or more. This reduces the deflection of its own weight and facilitates handling when a large substrate is formed.
• the specific elastic modulus is more preferably 34.5 MN ⁇ m / kg or more, further preferably 34.8 MN ⁇ m / kg or more, particularly preferably 35 MN ⁇ m / kg or more, and most preferably 35.2 MN ⁇ m / kg or more.
• the large substrate is, for example, a substrate having at least one side of 1800 mm or more. At least one side of the large substrate may be, for example, 2000 mm or more, 2500 mm or more, 3000 mm or more, or 3500 mm or more.
• the density of the alkali-free glass of this embodiment is preferably 2.60 g / cm 3 or less. This reduces the deflection of its own weight and facilitates handling when a large substrate is formed. Moreover, the device using the alkali-free glass of this embodiment can be reduced in weight. Density is more preferably 2.59 g / cm 3 or less, more preferably 2.58 g / cm 3 or less, particularly preferably 2.57 g / cm 3 or less, 2.56 g / cm 3 or less is most preferred.
• the glass surface devitrification viscosity ( ⁇ c ), which is the viscosity at the glass surface devitrification temperature (T c ) of the alkali-free glass of the present embodiment, is preferably 10 3.8 dPa ⁇ s or more. Thereby, it is excellent in the moldability of a glass substrate. Moreover, it can suppress that the crystal
• the glass surface devitrification viscosity ( ⁇ c ) is more preferably 10 3.85 dPa ⁇ s or more, further preferably 10 3.9 dPa ⁇ s or more, particularly preferably 10 4 dPa ⁇ s or more, and most preferably 10 4. 05 dPa ⁇ s or more.
• the temperature T 2 at which the viscosity of the alkali-free glass of this embodiment is 10 2 dPa ⁇ s is preferably 1680 ° C. or lower. Thereby, it is excellent in the solubility of glass. Moreover, this can reduce the burden on the manufacturing equipment. For example, the lifetime of a kiln or the like that melts glass can be extended, and productivity can be improved. In addition, this makes it possible to reduce kiln-derived defects (for example, defects and Zr defects).
• T 2 is more preferably 1670 ° C. or less, further preferably 1660 ° C. or less, particularly preferably 1640 ° C. or less, particularly preferably 1635 ° C. or less, and most preferably 1625 ° C. or less.
• the glass transition point of the alkali-free glass of this embodiment is preferably 730 to 790 ° C.
• the glass moldability is excellent. For example, thickness deviation and surface waviness can be reduced.
• the glass transition point is 790 ° C. or less, the burden on the production facility can be reduced. For example, the surface temperature of the roll used for glass molding can be lowered, the life of the equipment can be extended, and productivity can be improved.
• the glass transition point is more preferably 740 ° C. or higher, further preferably 745 ° C. or higher, particularly preferably 750 ° C. or higher, and most preferably 755 ° C. or higher.
• the glass transition point is more preferably 785 ° C. or less, further preferably 783 ° C. or less, particularly preferably 780 ° C. or less, and most preferably 775 ° C. or less.
• the compaction of the alkali-free glass of this embodiment is preferably 100 ppm or less, more preferably 90 ppm or less, further preferably 80 ppm or less, further preferably 75 ppm or less, particularly preferably 70 ppm or less, and most preferably 65 ppm or less.
• Compaction is the glass heat shrinkage generated by relaxation of the glass structure during the heat treatment.
• the compaction in this embodiment means the compaction measured in the following procedure.
• a glass plate sample obtained by processing the alkali-free glass of the present embodiment (a sample having a length of 100 mm, a width of 10 mm, and a thickness of 1 mm mirror-polished with cerium oxide) at a temperature of glass transition point + 120 ° C. for 5 minutes. Cool to room temperature at 40 ° C. per minute. When the glass plate sample is cooled to room temperature, the total length (length direction) L1 of the sample is measured. Thereafter, the glass plate sample is heated to 600 ° C. at 100 ° C./hour, held at 600 ° C. for 80 minutes, and cooled to room temperature at 100 ° C./hour. When the glass plate sample is cooled to room temperature, the total length L2 of the sample is measured again. The ratio (L1 ⁇ L2) / L1 between the difference in total length before and after the heat treatment at 600 ° C. (L1 ⁇ L2) and the total length L1 of the sample before the heat treatment at 600 ° C. is taken as the compaction value.
• the alkali-free glass of the present embodiment preferably has an equivalent cooling rate of 500 ° C./min or less, for example.
• the equivalent cooling rate is preferably 5 ° C./min or more and 500 ° C./min or less from the viewpoint of the balance between compaction and productivity. From the viewpoint of productivity, the equivalent cooling rate is more preferably 10 ° C./min or more, further preferably 15 ° C./min or more, particularly preferably 20 ° C./min or more, and most preferably 25 ° C./min or more.
• the equivalent cooling rate is more preferably 300 ° C./min or less, further preferably 200 ° C./min or less, particularly preferably 150 ° C./min or less, and most preferably 100 ° C./min or less.
• the equivalent cooling rate in this embodiment means the equivalent cooling rate measured in the following procedure. A plurality of 10 mm ⁇ 10 mm ⁇ 1 mm cuboidal calibration curve preparation samples obtained by processing the alkali-free glass of this embodiment are prepared, and these are prepared at 5 at a glass transition point + 120 ° C. using an infrared heating electric furnace. Hold for a minute. Thereafter, each sample is cooled to 25 ° C.
• the alkali-free glass of the present embodiment is processed into a rectangular parallelepiped 10 mm ⁇ 10 mm ⁇ 1 mm, measured by a V block method using a precision refractometer KPR-2000 of the n d Shimadzu devices manufactured.
• the alkali-free glass of this embodiment has a high Young's modulus of 88 GPa or higher and is suitable for a glass plate used as a large substrate because deformation of the substrate due to external stress is suppressed.
• the large substrate is, for example, a glass plate having at least one side of 1800 mm or more, and a specific example is a glass plate having a long side of 1800 mm or more and a short side of 1500 mm or more.
• the alkali-free glass of this embodiment is preferably a glass plate having at least one side of 2400 mm or more, for example, a glass plate having a long side of 2400 mm or more and a short side of 2100 mm or more, and a glass plate having at least one side of 3000 mm or more, for example, a long side of 3000 mm or more.
• a glass plate having a short side of 2800 mm or more particularly preferably a glass plate having at least one side of 3200 mm or more, for example, a glass plate having a long side of 3200 mm or more, a short side of 2900 mm or more, and a glass plate having at least one side of 3300 mm or more, for example, It is most preferable for a glass plate having a long side of 3300 mm or more and a short side of 2950 mm or more.
• the alkali-free glass of the present embodiment is preferable because the thickness is 0.7 mm or less because it is lightweight.
• the thickness of the alkali-free glass of the present embodiment is more preferably 0.65 mm or less, further preferably 0.55 mm or less, preferably 0.45 mm or less, and most preferably 0.4 mm or less.
• the thickness can be 0.1 mm or less, or 0.05 mm or less, the thickness is preferably 0.1 mm or more, and more preferably 0.2 mm or more from the viewpoint of preventing deflection due to its own weight.
• the alkali-free glass of this embodiment can be manufactured by the following procedures, for example.
• a glass raw material is prepared so as to have a desired glass composition, which is put into a melting furnace, heated to 1500 to 1800 ° C. and melted to obtain a molten glass.
• the obtained molten glass is formed into a glass ribbon having a predetermined plate thickness with a forming apparatus, and the glass ribbon is gradually cooled and then cut to obtain an alkali-free glass.
• the molten glass into a glass plate by a float method or a fusion method. From the viewpoint of stably producing a large plate glass having a high Young's modulus (for example, 1800 mm or more on one side), it is preferable to use a float method.
• the display panel of this embodiment has the alkali-free glass of this embodiment described above as a glass substrate.
• the display panel is not particularly limited as long as it has the alkali-free glass of the present embodiment, and may be various display panels such as a liquid crystal display panel and an organic EL display panel.
• a display surface electrode substrate in which a gate electrode line and a gate insulating oxide layer are formed on the surface, and a pixel electrode is formed on the oxide layer surface (Array substrate) and a color filter substrate having an RGB color filter and a counter electrode formed on the surface thereof, and a liquid crystal material is sandwiched between the array substrate and the color filter substrate that are paired with each other A cell is configured.
• the liquid crystal display panel includes other elements such as peripheral circuits.
• the alkali-free glass of this embodiment is used for at least one of a pair of substrates constituting the cell.
• the alkali-free glass of this embodiment can be used as a glass plate for supporting electronic devices, for example.
• a device such as a glass substrate, a silicon substrate, or a resin substrate on the alkali-free glass (glass plate for supporting an electronic device) of this embodiment.
• the device forming substrate is supported by bonding the forming substrate directly or by using an adhesive.
• a glass plate for supporting an electronic device for example, a supporting glass plate in a manufacturing process of a flexible display (for example, an organic EL display) using a resin such as polyimide as a substrate, and a resin-silicon chip composite wafer in a manufacturing process of a semiconductor package A glass plate etc. are mentioned.
• the semiconductor device of this embodiment has the alkali-free glass of this embodiment described above as a glass substrate.
• the semiconductor device of this embodiment has the alkali-free glass of this embodiment as a glass substrate for image sensors such as MEMS, CMOS, and CIS.
• the semiconductor device of this embodiment has the alkali-free glass of this embodiment as a cover glass for a display device for projection use, for example, a cover glass of LCOS (Liquid Crystal ON Silicon).
• LCOS Liquid Crystal ON Silicon
• the information recording medium of this embodiment has the alkali-free glass of this embodiment described above as a glass substrate.
• Specific examples of the information recording medium include a magnetic recording medium and an optical disk.
• Examples of the magnetic recording medium include an energy-assisted magnetic recording medium and a perpendicular magnetic recording magnetic recording medium.
• the planar antenna of this embodiment has the above-described alkali-free glass of this embodiment as a glass substrate.
• Specific examples of the planar antenna of the present embodiment include a planar liquid crystal antenna having a planar shape such as a liquid crystal antenna or a microstrip antenna (patch antenna) as an antenna having good directivity and reception sensitivity.
• the liquid crystal antenna is disclosed in, for example, International Publication No. 2018/016398.
• the patch antenna is disclosed in, for example, Japanese National Publication No. 2017-509266 and Japanese Unexamined Patent Publication No. 2017-063255.
• Examples 1 to 12 and Examples 19 to 36 are examples, and Examples 13 to 18 are comparative examples.
• the raw materials of each component were prepared so that the glass composition became the composition shown in Tables 1 to 6 (unit: mol%), and melted at 1600 ° C. for 1 hour using a platinum crucible. After melting, the melt was poured onto a carbon plate, held at a temperature of glass transition point + 30 ° C. for 60 minutes, and then cooled to room temperature (25 ° C.) at 1 ° C./min to obtain a plate glass. This was mirror polished to obtain a glass plate, and various physical properties were measured. The results are shown in Tables 1 to 6. In Tables 1 to 6, the values shown in parentheses are calculated values, and the blanks are not measured.
• the measuring method of each physical property is shown below.
• (Average thermal expansion coefficient) According to the method prescribed
• TMA differential thermal dilatometer
• the measurement temperature range was room temperature to 400 ° C. or higher, and the average thermal expansion coefficient at 50 to 350 ° C. was expressed as a unit of 10 ⁇ 7 / ° C.
• density According to the method defined in JIS Z 8807, the density of about 20 g of glass lump containing no foam was measured by the Archimedes method.
• strain point The strain point was measured by the fiber drawing method according to the method defined in JIS R3103-2 (2001).
• Glass transition point Tg The glass transition point Tg was measured by the thermal expansion method according to the method specified in JIS R3103-3 (2001).
• Young's modulus According to the method defined in JIS Z 2280, Young's modulus of glass having a thickness of 0.5 to 10 mm was measured by an ultrasonic pulse method.
• T 2 According to the method prescribed in ASTM C 965-96, the viscosity was measured using a rotational viscometer, and the temperature T 2 (° C.) when it reached 10 2 d ⁇ Pa ⁇ s was measured.
• T 4 According to the method prescribed in ASTM C 965-96, the viscosity was measured using a rotational viscometer, and the temperature T 4 (° C.) when it reached 10 4 d ⁇ Pa ⁇ s was measured.
• Devitrification temperature The glass was crushed and classified using a test sieve so that the particle size was in the range of 2 to 4 mm.
• the obtained glass cullet was ultrasonically washed in isopropyl alcohol for 5 minutes, washed with ion-exchanged water, dried, placed in a platinum dish, and subjected to heat treatment for 17 hours in an electric furnace controlled at a constant temperature. went.
• the temperature of the heat treatment was set at 10 ° C. intervals.
• the glass was removed from the platinum dish, and the maximum temperature at which crystals were deposited and the minimum temperature at which crystals were not deposited were measured using an optical microscope.
• the maximum temperature at which crystals precipitate on the surface and inside of the glass and the minimum temperature at which crystals do not precipitate were each measured once (when it was difficult to judge crystal precipitation, they were measured twice).
• T c The average value of the maximum temperature at which crystals precipitate on the glass surface and the minimum temperature at which crystals do not precipitate was determined and used as the glass surface devitrification temperature (T c ). Similarly, the average value of the maximum temperature at which crystals precipitate inside the glass and the minimum temperature at which crystals do not precipitate was determined and used as the glass internal devitrification temperature (T d ).
• the specific modulus was obtained by dividing the Young's modulus obtained by the above-described procedure by the density.
• the glass surface devitrification temperature (T c ) was determined by the method described above, and the viscosity of the glass at the glass surface devitrification temperature (T c ) was measured to obtain the glass surface devitrification viscosity ( ⁇ c ).
• glass internal devitrification temperature ( Td ) was calculated
• Al 2 O 3 is less than 12.5%, B 2 O 3 is more than 3%, MgO is less than 8%, CaO is less than 6%, SrO is more than 4%, RO is less than 18, and MgO / CaO is 1.33.
• ultra example 13 is less than 88GPa Young's modulus is low, T 4 was higher 1290 ° C. greater.
• T c glass surface devitrification temperature
• Example 16 in which SiO 2 is less than 62%, Al 2 O 3 is less than 12.5%, MgO is more than 13%, CaO is more than 12%, SrO is 0%, and RO is more than 22 has a large average thermal expansion coefficient. It was over 43 ⁇ 10 ⁇ 7 / ° C.
• the alkali-free glass of the present invention having the above-described features is suitable for uses such as a display substrate, a photomask substrate, an electronic device support substrate, an information recording medium substrate, and a planar antenna substrate.

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